US3996197A - Method of preparing polybenoxazindione polymers from aminophenoxy salicyclic acid compounds - Google Patents
Method of preparing polybenoxazindione polymers from aminophenoxy salicyclic acid compounds Download PDFInfo
- Publication number
- US3996197A US3996197A US05/537,664 US53766474A US3996197A US 3996197 A US3996197 A US 3996197A US 53766474 A US53766474 A US 53766474A US 3996197 A US3996197 A US 3996197A
- Authority
- US
- United States
- Prior art keywords
- aminophenoxy
- acid
- salicylic acid
- salicyclic
- salicyclic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- -1 aminophenoxy salicyclic acid compounds Chemical class 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 title description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UKKPABHOLOIDBI-UHFFFAOYSA-N phenyl 4-(4-aminophenoxy)-2-hydroxybenzoate Chemical compound C1=CC(N)=CC=C1OC(C=C1O)=CC=C1C(=O)OC1=CC=CC=C1 UKKPABHOLOIDBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- WVEAJOBRXVTWMF-UHFFFAOYSA-N 5-(4-acetamidophenoxy)-2-hydroxybenzoic acid Chemical compound C1=CC(NC(=O)C)=CC=C1OC1=CC=C(O)C(C(O)=O)=C1 WVEAJOBRXVTWMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- TXQQDHGSGMFBDZ-UHFFFAOYSA-N 2-hydroxy-5-(4-nitrophenoxy)benzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(OC=2C=CC(=CC=2)[N+]([O-])=O)=C1 TXQQDHGSGMFBDZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KWMGSVQJQHXTAS-UHFFFAOYSA-N phenyl 5-(4-aminophenoxy)-2-hydroxybenzoate Chemical compound C1=CC(N)=CC=C1OC1=CC=C(O)C(C(=O)OC=2C=CC=CC=2)=C1 KWMGSVQJQHXTAS-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- SPENOWPHMBDRAJ-UHFFFAOYSA-N 3-amino-2-phenylperoxybenzoic acid Chemical class NC1=CC=CC(C(O)=O)=C1OOC1=CC=CC=C1 SPENOWPHMBDRAJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- FOIVBYJXOZPFPA-UHFFFAOYSA-N 2-hydroxy-4-(4-nitrophenoxy)benzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 FOIVBYJXOZPFPA-UHFFFAOYSA-N 0.000 description 2
- BMPBMQJHDJMYJL-UHFFFAOYSA-N 2-hydroxy-5-(2-nitrophenoxy)benzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(OC=2C(=CC=CC=2)[N+]([O-])=O)=C1 BMPBMQJHDJMYJL-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- HNJVADWGECCHQA-UHFFFAOYSA-N 5-(2-chloro-4-nitrophenoxy)-2-hydroxybenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)[N+]([O-])=O)Cl)=C1 HNJVADWGECCHQA-UHFFFAOYSA-N 0.000 description 2
- AARXDBMVEVHGJT-UHFFFAOYSA-N 5-(4-aminophenoxy)-2-hydroxybenzoic acid Chemical compound C1=CC(N)=CC=C1OC1=CC=C(O)C(C(O)=O)=C1 AARXDBMVEVHGJT-UHFFFAOYSA-N 0.000 description 2
- POCQWBOLSDZIEC-UHFFFAOYSA-N 5-(4-chloro-2-nitrophenoxy)-2-hydroxybenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(OC=2C(=CC(Cl)=CC=2)[N+]([O-])=O)=C1 POCQWBOLSDZIEC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- RZKKOBGFCAHLCZ-UHFFFAOYSA-N 1,4-dichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC=C1Cl RZKKOBGFCAHLCZ-UHFFFAOYSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- ARANIOOHQZVUES-UHFFFAOYSA-N 5-(2-amino-4-chlorophenoxy)-2-hydroxybenzoic acid Chemical compound NC1=CC(Cl)=CC=C1OC1=CC=C(O)C(C(O)=O)=C1 ARANIOOHQZVUES-UHFFFAOYSA-N 0.000 description 1
- KCWVJARCXFGZAX-UHFFFAOYSA-N 5-(2-aminophenoxy)-2-hydroxybenzoic acid Chemical compound NC1=CC=CC=C1OC1=CC=C(O)C(C(O)=O)=C1 KCWVJARCXFGZAX-UHFFFAOYSA-N 0.000 description 1
- MTQJGYXKWSWJBI-UHFFFAOYSA-N 5-(4-amino-2-chlorophenoxy)-2-hydroxybenzoic acid Chemical compound ClC1=CC(N)=CC=C1OC1=CC=C(O)C(C(O)=O)=C1 MTQJGYXKWSWJBI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FQZPTQLDTIDICW-UHFFFAOYSA-N phenyl 2-hydroxy-4-(4-nitrophenoxy)benzoate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C(O)=CC=1OC1=CC=C([N+]([O-])=O)C=C1 FQZPTQLDTIDICW-UHFFFAOYSA-N 0.000 description 1
- KOKOYFPGFUWVCS-UHFFFAOYSA-N phenyl 2-hydroxy-5-(4-nitrophenoxy)benzoate Chemical compound C1=C(C(=O)OC=2C=CC=CC=2)C(O)=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 KOKOYFPGFUWVCS-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
Definitions
- This invention relates to novel aminophenoxy salicylic acid compounds corresponding to the general formula: ##STR1## in which R represents a hydrogen atom, a C 1 to C 4 alkyl radical, a C 7 to C 10 aralkyl radical or a one-linkage C 6 to C 10 aromatic radical:
- R' represents a hydrogen atom, an aliphatic C 2 to C 5 acyl radical, an aromatic C 7 to C 10 acyl radical, a carboxylate radical COOR" where R" represents an alkyl radical having 1 to 4 carbon atoms, or a C 7 to C 10 aralkyl radical and
- X and Y same or different, represent a hydrogen atom, chlorine, bromine or a C 1 to C 4 alkyl radical.
- R means preferably a methyl, ethyl, isopropyl, n-propyl, n-(iso-, t-)butyl radical, a phenylmethyl, phenylethyl, phenylpropyl or phenylbutyl radical, a phenyl or naphthyl radical. Most preferably R means a hydrogen atom or a phenyl radical.
- R' is derived preferably from a radical of the general formula CH 3 (CH 2 ) n CO--, wherein n is a whole number from 0 to 3, from a radical of the general formula C 6 H 5 (CH 2 ) n CO--, wherein n is a whole number from 0 to 2, or from a carboxylate radical having the general formula --COOR", wherein R" means a methyl, ethyl, n-(sio-)-propyl, n-(iso-, t-)butyl, phenylmethyl, phenylpropyl or phenylbutyl radical. Most preferably R' means a hydrogen atom or an acetyl radical.
- R' represents COOR" as defined above and R, X and Y are defined as above.
- X represents chlorine, bromine or a C 1 to C 4 alkyl radical and R, R' and Y are defined as above.
- aminophenoxy salicyclic acids according to the invention are produced from the corresponding nitrophenoxy salicyclic acids by reducing nitro compounds in the presence of known catalysts to amino compounds by conventional methods, acylating and esterifying the amino compounds with anhydrides, carboxylic acid chlorides and with chlorocarbonic acid esters. For this reason, there are a number of possible known methods of producing N-acylated aminophenoxy salicyclic acid esters, depending upon the order in which the individual reaction stages are carried out.
- aminophenoxy salicyclic acid compounds according to the invention represent excellent intermediate products for the production of plastics, resistant to high temperatures, for example aromatic polyamides, or preferably high-temperature-resistant polybenz-1,3-oxazin-(2,4)-diones, which are obtained by condensing the products with derivatives of carbonic acid.
- This polycondensation into high molecular weight polybenz-1,3-oxazin-(2,4)-diones can be carried out in the presence or absence of solvents.
- polycondensation is carried out in an aprotic, highly polar solvent, for example, N,N-dimethyl formamide; N,N-dimethyl acetamide; N,N,N',N'-tetramethyl urea; N,N,N',N',N",N"-hexamethyl phosphoric acid triamide; tetramethylene sulphone; diphenyl sulphoxide; or dimethyl sulphoxide.
- an aprotic, highly polar solvent for example, N,N-dimethyl formamide; N,N-dimethyl acetamide; N,N,N',N'-tetramethyl urea; N,N,N',N',N",N"-hexamethyl phosphoric acid triamide; tetramethylene sulphone; diphenyl sulphoxide; or dimethyl sulphoxide.
- the aprotic, highly polar solvents can also be used in admixture with one another or in conjunction with other aprotic, less polar solvents such as, for example, benzene, toluene, chlorobenzene, methylene chloride, carbon tetrachloride or dioxan.
- Dimethyl sulphoxide in which polycondensation takes place smoothly and quickly, is the preferred solvent.
- the polycondensation is carried out at temperatures from 150° - 300° C, preferably at temperatures from 180° - 250° C.
- the derivatives of carbonic acid used are the aliphatic esters, aromatic ester or the acid halogenide.
- the polymers according to the invention are particularly suitable for the production of films, resistant to high temperatures.
- 4-(4-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from p-chloronitrobenzene and 2,4-dihydroxybenzoic acid.
- 4-(4-nitrophenoxy)-salicylic acid phenyl ester was prepared in accordance with Example 1b by esterifying 4-(4-nitrophenoxy)-salicylic acid with diphenyl carbonate.
- 4-(4-aminophenoxy)-salicylic acid phenyl ester was prepared in accordance with Example 1c by hydrogenating 4-(4-aminophenoxy)-salicylic acid phenyl ester.
- 5-(2-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from 2-chloronitrobenzene and 2,5-dihydroxybenzoic acid.
- 5-(2-chloro-4-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from 2,5-dihydroxy-benzoic acid and 3,4-dichloronitrobenzene.
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Abstract
New aminophenoxy salicyclic acid compounds which can be used to prepare polybenz-oxazin dione.
Description
This invention relates to novel aminophenoxy salicylic acid compounds corresponding to the general formula: ##STR1## in which R represents a hydrogen atom, a C1 to C4 alkyl radical, a C7 to C10 aralkyl radical or a one-linkage C6 to C10 aromatic radical:
R' represents a hydrogen atom, an aliphatic C2 to C5 acyl radical, an aromatic C7 to C10 acyl radical, a carboxylate radical COOR" where R" represents an alkyl radical having 1 to 4 carbon atoms, or a C7 to C10 aralkyl radical and
X and Y, same or different, represent a hydrogen atom, chlorine, bromine or a C1 to C4 alkyl radical.
R means preferably a methyl, ethyl, isopropyl, n-propyl, n-(iso-, t-)butyl radical, a phenylmethyl, phenylethyl, phenylpropyl or phenylbutyl radical, a phenyl or naphthyl radical. Most preferably R means a hydrogen atom or a phenyl radical.
R' is derived preferably from a radical of the general formula CH3 (CH2)n CO--, wherein n is a whole number from 0 to 3, from a radical of the general formula C6 H5 (CH2)n CO--, wherein n is a whole number from 0 to 2, or from a carboxylate radical having the general formula --COOR", wherein R" means a methyl, ethyl, n-(sio-)-propyl, n-(iso-, t-)butyl, phenylmethyl, phenylpropyl or phenylbutyl radical. Most preferably R' means a hydrogen atom or an acetyl radical.
Most preferably R' represents COOR" as defined above and R, X and Y are defined as above.
Also most preferably X represents chlorine, bromine or a C1 to C4 alkyl radical and R, R' and Y are defined as above.
As representatives of the new compounds are mentioned:
4-(2-aminophenoxy)-salicyclic acid (phenylester)
5-(4-aminophenoxy)-salicyclic acid (phenylester)
5-(2-aminophenoxy)-salicyclic acid (phenylester)
4-(4-aminophenoxy)-salicyclic acid (phenylester)
4-(4-acetaminophenoxy)-salicyclic acid (phenylester)
5-(4-acetaminophenoxy)-salicyclic acid (phenylester)
5-(2-acetaminophenoxy)-salicyclic acid (phenylester)
4-(2-chloro-4-aminophenoxy)-salicyclic acid (phenylester)
5-(2-chloro-4-aminophenoxy)-salicyclic acid (phenylester)
4-(4-chloro-2-aminophenoxy)-salicyclic acid (phenylester)
5-(4-chloro-2-aminophenoxy)-salicyclic acid (phenylester)
4-(2-aminophenoxy)-salicyclic acid (methylester)
5-(4-aminophenoxy)-salicyclic acid (ethylester)
5-(2-aminophenoxy)-salicyclic acid (propylester)
4-(4-aminophenoxy)-salicyclic acid (methylester)
4-(4-acetaminophenoxy)-salicyclic acid (propylester)
5-(4-acetaminophenoxy)-salicyclic acid (methylester)
5-(2-acetaminophenoxy)-salicyclic acid (ethylester)
4-(2-chloro-4-aminophenoxy)-salicyclic acid (propylester)
5-(2-chloro-4-aminophenoxy)-salicyclic acid (ethylester)
4-(4-chloro-2-aminophenoxy)-salicyclic acid (methylester)
5-(4-chloro-2-aminophenoxy)-salicyclic acid (propylester)
Starting compounds for the aminophenoxy salicyclic acids according to the invention and their derivatives are the corresponding nitrophenoxy salicyclic acid compounds of the kind described, for example, in German Offenlegungsschrift No. 1,902,929.
The aminophenoxy salicyclic acids according to the invention are produced from the corresponding nitrophenoxy salicyclic acids by reducing nitro compounds in the presence of known catalysts to amino compounds by conventional methods, acylating and esterifying the amino compounds with anhydrides, carboxylic acid chlorides and with chlorocarbonic acid esters. For this reason, there are a number of possible known methods of producing N-acylated aminophenoxy salicyclic acid esters, depending upon the order in which the individual reaction stages are carried out.
The aminophenoxy salicyclic acid compounds according to the invention represent excellent intermediate products for the production of plastics, resistant to high temperatures, for example aromatic polyamides, or preferably high-temperature-resistant polybenz-1,3-oxazin-(2,4)-diones, which are obtained by condensing the products with derivatives of carbonic acid. This polycondensation into high molecular weight polybenz-1,3-oxazin-(2,4)-diones can be carried out in the presence or absence of solvents. In its preferred form, polycondensation is carried out in an aprotic, highly polar solvent, for example, N,N-dimethyl formamide; N,N-dimethyl acetamide; N,N,N',N'-tetramethyl urea; N,N,N',N',N",N"-hexamethyl phosphoric acid triamide; tetramethylene sulphone; diphenyl sulphoxide; or dimethyl sulphoxide. The aprotic, highly polar solvents can also be used in admixture with one another or in conjunction with other aprotic, less polar solvents such as, for example, benzene, toluene, chlorobenzene, methylene chloride, carbon tetrachloride or dioxan. Dimethyl sulphoxide, in which polycondensation takes place smoothly and quickly, is the preferred solvent. The polycondensation is carried out at temperatures from 150° - 300° C, preferably at temperatures from 180° - 250° C. The derivatives of carbonic acid used are the aliphatic esters, aromatic ester or the acid halogenide.
The polymers according to the invention are particularly suitable for the production of films, resistant to high temperatures.
a. 77 g of 2,5-dihydroxybenzoic acid and 78.5 g of p-chloronitrobenzene were dissolved in 300 ml of dimethyl sulphoxide under a nitrogen atmosphere, and 40 g of sodium hydroxide and 225 ml of benzene were added to the resulting solution. The mixture was then distilled under reflux at 90° to 95° C on a water separator until no more water was separated off (about 2 hours). The benzene was distilled off in a water jet vacuum, the residue poured into 2.5 liters of water, the mixture acidified with concentrated hydrochloric acid while stirring vigorously, the crude, pale brown 5-(4-nitrophenoxy)-salicylic acid which was precipitated was filtered off under suction and washed acid free with water. Drying in vacuo at 80° C gave 126 g (92% of the theoretical yield) of 5-(4-nitrophenoxy)-salicylic acid, recrystallised from methanol (and active carbon, optionally with a little water added) 120 g (87% of the theoretical) of yellow crystals melting at 193° to 194° C.
b. 220 g of 5-(4-nitrophenoxy)-salicylic acid and 21.9 g of imidazole were added at 75° C to a mixture, melted under nitrogen, of 343 g of diphenyl carbonate and 220 g of phenol, the mixture was stirred at 150° C until no more carbon dioxide was evolved (about 1 hour), 2 liters of ether were added to the solution after cooling to room temperature in order to precipitate the phenyl ester formed, the phenyl ester thus formed was filtered off under suction, washed with ether and dried in vacuo at 80° C. Yield 215 g 5-(4-nitrophenoxy)-salicyclic acid (77% of the theoretical yield) of m.p. 123° - 127° C and of m.p. 130° - 130.5° C after recrystallisation from benzene/gasoline.
Analysis: C19 H13 NO6 (351.30). Calculated: 65.0%, C; 3.73%, H; 3.99%, N. Found: 64.9, C; 3.71, H; 4.02, N.
c. 515 g of 5-(4-nitrophenoxy)-salicylic phenyl ester were dissolved in 1.5 liters of dioxan and hydrogenated in an autoclave at 55° to 75° C under a hydrogen pressure of 150 to 180 atms. following the addition of 10.3 g of palladium carbon (containing 5% of palladium). Hydrogenation took 2 hours. After the catalyst had been separated off, hydrogen chloride was introduced into the filtrate until it was saturated, resulting in the precipitation of the hydrochloride of 5-(4-aminophenoxy)-salicylic acid phenyl ester which was filtered off under suction, washed with dioxan and dried in vacuo at 70° C.
Yield: 438 g (84% of the theoretical yield) of hydrochloride.
Recrystallisation of the hydrochloride from ethanol/water gave the free 5-(4-aminophenoxy)-salicylic acid phenyl ester in the form of colourless needles melting at 119° C.
Analysis: C19 H15 NO4 (321.32). Calculated: 71.0%, C; 4.71%, H; 4.36%, N. Found: 70.9, C; 4.73, H; 4.68, N.
a. 35.75 g of the hydrochloride of 5-(4-aminophenoxy)-salicylic phenyl ester produced in accordance with Example 1c, were hydrolysed by boiling for 2 hours in a solution of 13.44 g of potassium hydroxide, 80 g of ethanol and 300 g of water. This was followed by acidification with approximately 55 ml of concentrated hydrochloric acid, the free amino acid which crystallised out was filtered off under suction after cooling and washed. After drying, the aminophenoxy salicylic acid was obtained in a substantially quantitative yield, melting at 224.5° to 225° C after recrystallisation from dimethyl formamide/water.
Analysis: C13 H11 NO4 (245.23). Calculated: 63.7%, C; 4.52%, H; 5.71%, N. Found: 63.4, C; 4.59, H; 5.88, N.
b. 71 g of 5-(4-nitrophenoxy)-salicylic acid prepared in accordance with Example 1a were hydrogenated at 90° C/100 atms. in 400 ml of ethanol or methanol in the presence of 2.8 g of Raney nickel. The adsorption of hydrogen ceased after 3 hours at the longest. Following the addition of 100 ml of dimethyl acetamide, the catalyst was separated off under heat, water was added at 100° C until a haze began to form, after which the solution was heated for 20 minutes in the presence of 20 g of active carbon and the free aminophenoxy salicylic acid allowed to crystallise out after filtration, being obtained in a yield of 50 g (79% of the theoretical yield), m.p. 223° - 224° C.
a. A solution of 1.4 g of acetyl chloride in 10 ml of dioxan was added dropwise over a period of 50 minutes at 25° C to a solution of 5 g of 5-(4-aminophenoxy)-salicylic acid, prepared in accordance with Example 2, and 1 g of sodium bicarbonate in 45 ml of dimethyl acetamide, stirring continued for 1 hour at room temperature and the reaction mixture was acidified with hydrochloric acid after it had been poured into 400 ml of water. The acetaminophenoxy alicylic acid separated off was filtered off under suction, washed and recrystallised from ethanol/water in the presence of active carbon. Yield 4 g (66% of the theoretical yield), m.p. 194° - 195° C.
Analysis: C15 H13 NO5 (287.26). Calculated: 62.7%, C; 4.56%, H; 4.88%, N. Found: 62.4, C; 4.54, H; 4.99, N.
b. production of polybenz-1,3-oxazin-(2,4)-diones
14,4 g of 5-(4-acetaminophenoxy)-salicyclic acid and 22 g of carbonic acid diphenylester were mixed and heated to 150 C under nitrogen atmosphere until the melt is clear. Then during one hour the reaction temperature is increased to about 220° to 250° C and the pressure decreased slowly about 1 torr. During this period the melt becomes more viscous and solidifies finally. The polybenz-1,3-oxazin-dione-(2,4) thus obtained was reduced to small pieces and extracted with methyl chloride. After the extraction 12,6 g (100% of theory) of the dried product was obtained having a relative viscosity = 1,22 (1 g polymer in 100 ml of a sulphuric acid solution).
a. 4-(4-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from p-chloronitrobenzene and 2,4-dihydroxybenzoic acid.
Yield: 63.5% of the theoretical yield, m.p. 193° - 195° C (from methanol).
Analysis: C13 H9 NO6 (275.21). Calculated: 56.7%, C; 3.30%, H; 5.09%, N. Found: 56.7, C; 3.27, H; 4.93, N.
b. 4-(4-nitrophenoxy)-salicylic acid phenyl ester was prepared in accordance with Example 1b by esterifying 4-(4-nitrophenoxy)-salicylic acid with diphenyl carbonate.
Yield: 60% of the theoretical yield, m.p. 118° - 119.5° C (from benzene/gasoline).
Analysis: C19 H13 NO6 (351.30). Calculated: 65.0%, C; 3.73%, H; 3.99%, N. Found: 65.0, C; 3.69, H; 3.90, N.
c. 4-(4-aminophenoxy)-salicylic acid phenyl ester was prepared in accordance with Example 1c by hydrogenating 4-(4-aminophenoxy)-salicylic acid phenyl ester.
Yield: quantitative in hydrochloride form; m.p. of the free amino ester 121° C (from ethanol/water).
Analysis: C19 H15 NO4 (321.32). Calculated: 71.0%, C; 4.71%, H; 4.36%, N. Found: 70.5, C; 4.61, H; 4.33, N.
d. production of polybenz-(1,3)-oxazin-dione-(2,4)
The reaction of 16 g of 4-(4-aminophenoxy)-salicyclic acid phenylester and of 22 g of carbonic acid diphenylester was carried out as described under Example 3b). 12,4 g (98% of the theory) of the polymer were obtained after extraction with methyl chloride. The polybenz-1,3-oxazin-dione-(2,4) thus obtained had a relative viscosity of 1,20 which was determined as described under 3b).
a. 5-(2-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from 2-chloronitrobenzene and 2,5-dihydroxybenzoic acid.
Yield: 94% of the theoretical yield, m.p. 173° - 174° C (from ethanol/water).
Analysis: C13 H9 NO6 (275.21). Calculated: 56.7%, C; 3.30%, H; 5.09%, N. Found: 56.8, C; 3.19, H; 5.13, N.
b. 5-(2-aminophenoxy)-salicylic acid was prepared in accordance with Example 2b from 5-(2-nitrophenoxy)-salicylic acid.
Yield: 89% of the theoretical yield, m.p. 233° C (from ethanol/acetone).
Analysis: C13 H11 NO4 (245.23). Calculated: 63.7%, C; 4.52%, H; 5.71%, N. Found: 63.3, C; 4.84, H; 5.95, N.
a. 5-(2-chloro-4-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from 2,5-dihydroxy-benzoic acid and 3,4-dichloronitrobenzene.
Yield: 86% of the theoretical yield, m.p. 204.5° - 205.5° C (from ethanol/acetone).
b. 5-(2-chloro-4-aminophenoxy)-salicylic acid was prepared in accordance with Example 2b from 5-(2-chloro-4-nitrophenoxy)-salicylic acid.
Yield: 89% of the theoretical yield, m.p. 208° - 209.5° C (from ethanol/acetone).
Analysis: C13 H10 ClNO4 (279.68). Calculated: 55.8%, C; 3.60%, H; 5.01%, N; 12.7%, Cl. Found: 55.7; C; 3.50, H; 5.42, N; 12.8, Cl.
a. 5-(4-chloro-2-nitrophenoxy)-salicylic acid was prepared in accordance with Example 1a from 2,5-dihydroxy-benzoic acid and 2,5-dichloronitrobenzene.
Yield: 85% of the theoretical yield, m.p. 228.5° - 230° C (from ethanol/water).
Analysis: C13 H8 ClNO6 (309.66). Calculated: 50.4%, C; 2.60%, H; 4.52%, N; 11.5%, Cl. Found: 50.4, C; 2.79, H; 4.91, N; 11.5, Cl
b. 5-(4-chloro-2-aminophenoxy)-salicylic acid was prepared in accordance with Example 2b from 5-(4-chloro-2-nitrophenoxy)-salicylic acid.
Yield: 85% of the theoretical yield, m.p. 225° - 226° C. (from ethanol/water).
Analysis: C13 H10 ClNO4 (279.68). Calculated: 55.8%, C; 3.60%, H; 5.01%, N; 12.7%, Cl. Found: 55.8, C; 3.62, H; 5.15, N; 12.7, Cl
Claims (5)
1. A process for the production of polybenz-1,3-oxazin(2,4)-diones, which comprises polycondensing at 150°-300° C.
1. an aminophenoxy salicylic acid compound of the formula: ##STR2## wherein R is hydrogen, C1 --C4 -alkyl, phenyl-C1 --C4 -alkyl, phenyl, or naphthyl;
R' is hydrogen, C1 --C4 -alkyl carbonyl, phenylcarbonyl, phenyl-C1 --C2 -alkyl carbonyl, C1 --C4 -alkoxycarbonyl, or phenyl-C1 --C4 -alkoxycarbonyl; and
X and Y, independently of each other, are hydrogen, chloro, bromo, or C1 --C4 -alkyl; with
2.
2. carbonic acid, aliphatic carbonate, aromatic carbonate, or halide. 2. The process of claim 1 wherein R is hydrogen or phenyl.
3. The process of claim 1 wherein R' is hydrogen or acetyl.
4. The process of claim 1 wherein said aminophenoxy salicylic acid compound is polycondensed with carbonic acid diphenyl ester.
5. The process of claim 1 wherein 5-(4-acetaminophenoxy)-salicylic acid or 4-(4-aminophenoxy)-salicylic acid phenyl ester is polycondensed with carbonic acid diphenyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/537,664 US3996197A (en) | 1972-07-01 | 1974-12-31 | Method of preparing polybenoxazindione polymers from aminophenoxy salicyclic acid compounds |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DT2232462 | 1972-07-01 | ||
| DE19722232462 DE2232462A1 (en) | 1972-07-01 | 1972-07-01 | AMINOPHENOXY-SALICYLIC ACID COMPOUNDS |
| US37487873A | 1973-06-29 | 1973-06-29 | |
| US05/537,664 US3996197A (en) | 1972-07-01 | 1974-12-31 | Method of preparing polybenoxazindione polymers from aminophenoxy salicyclic acid compounds |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US37487873A Continuation-In-Part | 1972-07-01 | 1973-06-29 |
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| US3996197A true US3996197A (en) | 1976-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/537,664 Expired - Lifetime US3996197A (en) | 1972-07-01 | 1974-12-31 | Method of preparing polybenoxazindione polymers from aminophenoxy salicyclic acid compounds |
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| US (1) | US3996197A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125519A (en) * | 1976-10-13 | 1978-11-14 | Murray Goodman | Polypeptides containing 3,4-dihydroxyphenylalanine |
| US4920198A (en) * | 1987-06-17 | 1990-04-24 | Enichem Tecnoresine S.P.A. | Branched polycarbonate from hydroxy-naphthoic acid or derivative, and process for preparing |
| US6376080B1 (en) | 1999-06-07 | 2002-04-23 | Loctite Corporation | Method for preparing polybenzoxazine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2904537A (en) * | 1955-10-28 | 1959-09-15 | Du Pont | Polybenzoxazoles |
| US3230196A (en) * | 1962-08-06 | 1966-01-18 | Borg Warner | Thermally stable polybenzoxazoles |
| US3676399A (en) * | 1968-02-22 | 1972-07-11 | Nat Res Dev | Polybenzoxazole amides, esters and thioesters, polybenzthiazole amides, esters and, thioesters and preparation thereof |
-
1974
- 1974-12-31 US US05/537,664 patent/US3996197A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2904537A (en) * | 1955-10-28 | 1959-09-15 | Du Pont | Polybenzoxazoles |
| US3230196A (en) * | 1962-08-06 | 1966-01-18 | Borg Warner | Thermally stable polybenzoxazoles |
| US3676399A (en) * | 1968-02-22 | 1972-07-11 | Nat Res Dev | Polybenzoxazole amides, esters and thioesters, polybenzthiazole amides, esters and, thioesters and preparation thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125519A (en) * | 1976-10-13 | 1978-11-14 | Murray Goodman | Polypeptides containing 3,4-dihydroxyphenylalanine |
| US4920198A (en) * | 1987-06-17 | 1990-04-24 | Enichem Tecnoresine S.P.A. | Branched polycarbonate from hydroxy-naphthoic acid or derivative, and process for preparing |
| US6376080B1 (en) | 1999-06-07 | 2002-04-23 | Loctite Corporation | Method for preparing polybenzoxazine |
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